The instant invention provides the cyclohexenyl-alpha-alkyl acrolein derivatives defined according to the generic structure: ##STR3## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent hydrogen or methyl with the proviso that one, two or three of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent methyl; wherein R.sub.5 represents methyl or ethyl; wherein one of the dashed lines represents a carbon-carbon double bond and the other of the dashed lines represents a carbon-carbon single bond; wherein the wavy lines represent the "cis" or "trans" juxtaposition of the moieties hydrogen, R.sub.5, cyclohexenyl and carboxaldehyde about the carbon-carbon double bond; and uses thereof for their organoleptic properties in consumable materials.
Materials which provide powerful, green, cumin-like, spicy, cinnamon-like, natural orris, floral (violet-like), animalic, musky, floral (lily/lilac), ionone-like, orris-like, burnt orris, pungent fresh green, woody and "tropical rain forest" aromas are highly desirable in the art of perfumery. Many of the natural materials which provide such fragrances and contribute such desired nuances to perfumery compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
By the same token, materials which can provide powerful, spicy, cinnamon, cumin-like, green and dandelion leaf-like aroma and taste nuances are highly desirable in the art of flavorings for foodstuffs, toothpastes, chewing gums, chewing tobaccos and medicinal products. Many of the natural materials which provide such flavor notes and contribute such desired nuances to flavoring compositions are high in costs, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
Hay-clover-like, sweet, rich-tobacco, floral, fruity, green and earthy aroma and taste nuances are highly desirable for many uses in flavoring smoking tobacco compositions and smoking tobacco article components.
Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)", Volume II, at monograph 2896, discloses that tetrahydro cinnamic aldehyde having the structure: ##STR4## has a powerful, sweet-green, leafy, delicately creamy odor. Arctander further discloses:
"The title aldehyde, commonly referred to under the title name, was developed many years ago in continuation of the search for interesting aldehydes from the Claisen reaction, by which Cinnamic aldehyde has been produced. It was also based upon a new method of obtaining Cyclohexene aldehydes and homologues of same. PA1 The subject material has found some application in perfumery, and so has the Cyclohexene carboxaldehyde from which it is made. The parent cyclic aldehyde has a powerful green-leafy odor, and it was interesting to see what type odor could be obtained by the Claisen condensation. PA1 Although rarely offered under its proper chemical name, this material is still used in various perfume specialties and bases for its refreshing, green note, sometimes useful in Citrus compositions, but also used in Chypres, Fougeres, etc. in combination with Oakmoss, Lavender, etc. PA1 It is produced from Acrolein and Butadiene to make Cyclohex-3-enealdehyde. By condensation (Claisen) with Acetaldehyde the title material is obtained." PA1 Finds use in perfume compositions where it blends excellently with Oakmoss products (compensates for sweetness and lifts the topnote), with Ionones (freshness), Geranium and Galbanum (enhances the green and "vegetable" notes), etc. PA1 On account of its modest cost it also finds its way into masking odors for industrial purposes. Its power compensates for its cost (usually slightly less than Citral) for such purposes. PA1 Produced by a Diels-Alder type condensation of 2-Methyl-2,4-pentadiene and Crotonaldehyde. The reaction product is a mixture of isomers commercially called iso-Cyclocitral (after rectification)". PA1 "Mild floral-woody, somewhat oily-herbaceous odor, remotely reminiscent of Rose with similarity to the odor of hydrogenated Ionones. PA1 Suggested for use in perfume compositions. It brings a certain amount of floral lift to Rose compositions, and performs fairly well even in soap. However, the cost of the rarely offered and never readily available lots are rather discouraging to the perfumer, and it is most conceivable that this material can be left out of the perfumer's library without any great loss. PA1 Produced from alpha-Cyclocitral and Acetaldehyde by condensation." PA1 763: beta-Cyclocitrylidene Acetaldehyde . . . . PA1 "Sweet-woody, rather heavy odor, resembling that of beta-Ionone. More fruity than really floral, but not as tenacious as the Ionone. PA1 Suggested for use in perfume compositions, but since it does not offer any new or unusual odor characteristics, and it cannot be produced in economical competition to beta-Ionone, there is little or no chance that it will ever become a standard shelf ingredient for the perfumer. PA1 Produced from beta-Cyclocitral and Acetaldehyde by condensation."
Arctander, at monograph 2896, refers to French Pat. No. 672025 published on Dec. 21, 1929. In said French Pat. No. 672025, the Diels-Alder reactions of acrolein derivatives with conjugated dienes to produce cyclohexene carboxaldehydes are disclosed. Thus, for example, the reaction: ##STR5## is disclosed to produce a perfumery compound. Furthermore, French Pat. No. 672025 discloses that the resulting carboxaldehydes can be further reacted with ketones to produce irone-type derivatives at page 3, lines 75-82 and at page 4, lines 1-5.
Neither the French Pat. No. 672025 nor the Arctander reference discloses or infers that the compounds defined according to the structure: ##STR6## has desirable organoleptic properties which are unexpected, unobvious and advantageous.
Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)", Volume I, at monograph 761 discloses the use of iso-Cyclocitral which is a mixture of compounds having the structures: ##STR7## for its organoleptic properties thusly: "Powerful, and diffusive, foilage-green, "dark"-weedy and dry odor, sometimes described as "Flower-shop odor". The earthy and wet-green notes are quite natural in high dilution and resemble the odor of stems from plants and flowers fresh from the soil.
At monographs 762 and 763, Arctander describes alpha-Cyclocitrylidene Acetaldehyde and beta-Cyclocitrylidene Acetaldehyde having the structures, respectively: ##STR8## thusly: 762: alpha-Cyclocitrylidene Acetaldehyde . . . .
U.S. Pat. No. 3,031,507 discloses the use in perfumery of cyclohexylcrotonaldehyde having the structure: ##STR9##
U.S. Pat. No. 3,313,843 discloses the use of cinnamaldehyde derivatives having the structure: ##STR10## wherein R is hydrogen or methyl as intermediates for preparing other compounds.
Nothing in the prior art, above cited, or any other prior art infers or discloses the compounds having the generic structure: ##STR11## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent hydrogen or methyl with the proviso that one, two or three of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent methyl; wherein R.sub.5 represents methyl or ethyl; wherein one of the dashed lines represents a carbon-carbon double bond and the other of the dashed lines represents a carbon-carbon single bond; wherein the wavy lines represent the "cis" or "trans" juxtaposition of the moieties hydrogen, R.sub.5, cyclohexenyl and carboxaldehyde about the carbon-carbon double bond.
Nothing in the prior art discloses that such compounds having the structure: ##STR12## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent hydrogen or methyl with the proviso that one, two or three of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 represent methyl; wherein R.sub.5 represents methyl or ethyl; wherein one of the dashed lines represents a carbon-carbon double bond and the other of the dashed lines represents a carbon-carbon single bond; wherein the wavy lines represent the "cis" or "trans" juxtaposition of the moieties hydrogen, R.sub.5, cyclohexenyl and carboxaldehyde about the carbon-carbon double bond; has such unexpected, unobvious and advantageous organoleptic properties.